Production of OH3+ salts

ABSTRACT

Strong Lewis acids added to wet HF protonate the water to form stable OH 3   +  salts.

The invention herein described was made in the course of or under a contract or subcontract thereunder, (or grant) with the United States Navy.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 767,010 filed Feb. 9, 1977 now abandoned, which is a continuation-in-part of Ser. No. 625,398 filed Oct. 24, 1975, and since abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to compositions of matter and methods of producing the same. More particularly, the present invention relates to stable OH₃ ⁺ salts and methods of producing such salts by protonation of water from wet HF.

2. Description of the Prior Art

Hydrogen fluoride (FH) is widely used as a very good, inert, solvent. However, if the HF becomes wet, the water contained therein often tends to hydrolize the intended compounds. This destroys the compounds, sometimes with explosive results.

Numberous methods have been proposed heretofore for removing water from HF. Thus, it is known to react on alkali metal fluoride with HF to form the corresponding bifluoride, dry the bifluoride and pyrolize the biflouride to recover dry FH. Similarly, it has been known to remove water from HF electrolytically, using alternating current. Moreover, it has been known to treat HF with high pressure fluorine to remove water from the HF. Unfortunately, all of these prior art methods of removing water from HF are complicated, timeconsuming and expensive. Furthermore, the latter method requires handling of gaseous fluorine under pressure which is quite hazardous to undertake.

BRIEF SUMMARY AND OBJECTS OF THE INVENTION

These disadvantages of the prior art are overcome with the present invention and a novel method of removing water from HF is proposed which is simple, fast, inexpensive and safe. Moreover, the method of the present invention yields a by-product which is useful and valuable.

The advantages of the present invention are preferably attained by adding a strong Lewis acid to wet HF to protonate the water into a solid, non-volatile residue. This residue is found to be an OH₃ ⁺ salt, which is a strong solid acid and which is highly useful as a polymerization catalyst. The OH₃ ⁺ salts are easily transported, are non-corrosive and are much safer to store and use than the liquid acids for which they may be substituted.

Accordingly, it is an object of the present invention to provide an improved method of removing water from HF.

Another object of the present invention is to provide a method of removing water from HF which method is simple, fast, economical and safe.

An additional object of the present invention is to provide a composition of matter which is a strong solid acid.

A further object of the present invention is to provide a composition of matter which is a strong solid acid which is highly useful as a polymerization catalyst.

Another object of the present invention is to provide a composition of matter which is a strong solid acid that is easily transported, non-corrosive, non-volatile, and safe to store and use.

A further object of the present invention is to provide stable OH₃ ⁺ salts as a new composition of matter.

An additional object of the present invention is to provide a method of producing stable OH₃ ⁺ salts.

A specific object of the present invention is the method of adding a strong Lewis acid to wet HF to protonate the water into a stable OH₃ ⁺ salt.

These and other objects and features of the present invention will be apparent from the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

In that form of the present invention chosen for purposes of illustration, a strong Lewis acid is added to wet HF to protonate the water into a stable OH₃ ⁺ salt. Suitable Lewis acids are SbF₅ or AsF₅.

EXAMPLE I Preparation of OH₃ ⁺ SbF₆ ⁻

In a typical experiment, SbF₅ (8.305 mmol) was placed in an ampoule and 8 ml of liquid anhydrous HF was added at -196° C. The mixture was warmed to 25° C to give a homogenous solution. Next, the ampoule was rechilled to -196° C and distilled water (8.30 mmol) was added. The mixture was then warmed to 25° C. Removal of all volatile material in vacuo at 25° C resulted in 2.116g of a white solid residue. The calculated weight for 8.30 mmol of OH₃ ⁺ SbF₆ ⁻ is 2.115g. Moreover, a calculated analysis for OH₃ ⁺ SbF₆ ⁻ yields H₂ O 7.07; Sb 47.8 spectral analysis of the aforementioned residue yielded H₂ O 6.93; Sb 48.0. The white solid was found to be stable up to 357° C, at which temperature it decomposed. The x-ray diffraction pattern for this material is shown in Table I.

                  TABLE I                                                          ______________________________________                                         X-Ray Powder Data for OH.sub.3.sup.+ SbF.sub.6.sup.-a                          d.sub.obsd, A                                                                           d.sub.calcd, A                                                                            Intens       h     k     1                                 ______________________________________                                         8.75     8.77       m            0     0     1                                 4.78     4.80       m            2     0     1                                 4.38     4.39       s            0     0     2                                 3.47     3.49       m            2     0     2                                 3.32     3.34        vs          2     1     2                                 2.868    2.869       mw          4     0     0                                 2.785    2.784      m            4     1     0                                 2.241    2.251      m            5     1     0                                 2.199    2.194      s            0     0     4                                                                  4     0     3                                 2.053    2.049       mw                                                                                         2     0     4                                 2.021    2.017      m            2     1     4                                 1.901    1.903       mw          3     0     4                                 1.877    1.877      m            3     1     4                                 1.779    1.777       mw          6     2     1                                 1.760    1.756      m            5     4     1                                 1.680    1.679       mw          6     3     1                                 1.663               m                                                          1.595                mw                                                        1.578               m                                                          1.515                vw                                                        1.505               w                                                          1.401                mw                                                        1.392               m                                                          1.347                mw                                                        1.341               m                                                          1.258                mw                                                        1.220               m                                                          1.187                mw                                                        1.155                mw                                                        1.100                mw                                                        1.075                mw                                                        1.052                mw                                                        1.030                mw                                                        1.010               m                                                          0.990               m                                                          0.972               w                                                          0.963                vw                                                        0.937               m                                                          0.922               m                                                          0.9072               mw                                                        0.8925              m                                                          0.8793              m                                                          0.8663              m                                                          0.8538              m                                                          0.8365               vw                                                        0.8306              m                                                          0.8251              w                                                          0.8195              m                                                          0.8144              w                                                          0.8091              w                                                          0.8037              w                                                          0.7988              m                                                          0.7890              m                                                          0.7880              w                                                          0.7794              m                                                          0.7786              w                                                          ______________________________________                                          .sup.a Tetragonal, a = 11.48 A, c = 8.78 A, V = 1157.1 A, Z = 8,               p.sub.calcd = 2.93 g cm.sup.-3, Cu Kα radiation, and Ni filter.    

EXAMPLE II Preparation of OH₃ ⁺ AsF₆ ⁻

In a typical experiment, H₂ O (5.421 mmol) and anhydrous HF (8 ml of liquid) were combined at -196° C in an ampoule, followed by warm-up to 25° C. Arsenic pentafluoride (5.427 mmol) was added to this mixture at -196° C and the contents of the ampoule were allowed to warm slowly to room temperature. Removal of volatile material at 25° C in vacuo resulted in 1.128g of a white solid residue. The calculated weight for 5.421 mmol of OH₃ ³⁰ AsF₆ ⁻ is 1.127g. Furthermore, spectral analysis of the residue yielded H₂ O 8.26; As 35.7, while the calculated analysis for OH₃ ⁺ AsF₆ ⁻ yields H₂ O 8.66; As 36.0. The white solid was found to be stable up to 193° C, at which temperature it decomposed. The x-ray diffraction pattern for the resulting material is shown in Table II.

                  TABLE II                                                         ______________________________________                                         X-Ray Powder Data for OH.sub.3.sup.+ AsF.sub.6.sup.-a                          d.sub.obsd, A                                                                           d.sub.calcd, A                                                                            Intens        h    k    1                                  ______________________________________                                         4.64     4.62        vs           1    1    1                                  4.01     4.00        vs           2    0    0                                  2.82     2.83       s             2    2    0                                  2.420    2.414      w             3    1    1                                  2.315    2.312      w             2    2    2                                  1.999    2.002      w             4    0    0                                  1.833    1.837      w             3    3    1                                  1.785    1.791       mw           4    2    0                                  1.636    1.634      m             4    2    2                                                                    5    1    1                                  1.542    1.541       mw                                                                                          3    3    3                                  1.414    1.416       vw           4    4    0                                  1.355    1.353      w             5    3    1                                                                    6    0    0                                  1.336    1.335      w                                                                                            4    4    2                                  1.267    1.266       vw           6    2    0                                  ______________________________________                                          .sup.a Cubic, a = 8.015 A, V=514.9 A.sup.3, Z = 4, ρ.sub.calcd =           2.890g                                                                         cm.sup.-3, Cu Kα radiation, and Ni filter                          

Further characterization of OH₃ ⁺ SbF₆ ⁻ and OH₃ ⁺ AsF₆ ⁻ may be found in an article entitled, "Novel Onium Salts. Synthesis and Characterization of OH₃ ⁺ SbF₆ ⁻ and OH₃ ⁺ AsF₆ ⁻ ", published in Inorganic Chemistry, Vol. 14, No. 9, p.2224, September 1975 and written by K. O. Christe, C. J. Schack and R. D. Wilson.

EXAMPLE III Preparation of Dry HF

Using the methods of either Example I or II, it is easy to separate dry HF from the OH₃ ⁺ salt by distillation, since HF boils at 20° C.

Thus, the methods of Examples I or II, coupled with the step of Example III, have dual utility, serving to remove water from HF and, also, serving to produce stable solid OH₃ ⁺ salts.

Obviously, numerous variations and modifications can be made without departing from the present invention. Accordingly, it should be clearly understood that the forms of the present invention described above are illustrative only and are not intended to limit the scope of the present invention. 

I claim:
 1. A composition of matter consisting of an OH₃ ⁺ cation, and an anion consisting of the hexafluoride of a material selected from the group consisting of antimony and arsenic.
 2. A composition of matter consisting of OH₃ ⁺ SbF₆ ⁻ as a white solid which is stable up to 357° C, at which temperature it decomposes.
 3. A composition of matter consisting of OH₃ ⁺ AsF₆ ⁻ as a white solid which is stable up to 193° C, at which temperature it decomposes. 